CN102280615A - Method for manufacturing positive active material for rechargeable lithium battery and rechargeable lithium battery using same - Google Patents

Method for manufacturing positive active material for rechargeable lithium battery and rechargeable lithium battery using same Download PDF

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CN102280615A
CN102280615A CN2011101363070A CN201110136307A CN102280615A CN 102280615 A CN102280615 A CN 102280615A CN 2011101363070 A CN2011101363070 A CN 2011101363070A CN 201110136307 A CN201110136307 A CN 201110136307A CN 102280615 A CN102280615 A CN 102280615A
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mixture
lithium
crucible
positive electrode
electrode active
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CN102280615B (en
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金民汉
朴度炯
权善英
宋有美
金志炫
金景眩
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Samsung SDI Co Ltd
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Samsung SDI Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/426—Fluorocarbon polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

A method for preparing a positive active material for a rechargeable lithium battery includes: a) providing a furnace and a crucible that is included in the furnace; b) putting a mixture of a composite metal precursor and a lithium compound into the crucible; and c) preparing a positive active material for a rechargeable lithium battery by firing the mixture in the crucible, wherein during the process b), the mixture in the crucible is positioned so that a minimum distance from a predetermined position inside the mixture to an exterior of the mixture in the crucible is about 5 cm or less. A rechargeable lithium made by this method is disclosed.

Description

Be used to make the method and the chargeable lithium cell of positive electrode active materials
Technical field
One embodiment of the present of invention relate to method and a kind of chargeable lithium cell that comprises this positive electrode active materials that a kind of preparation is used for the positive electrode active materials of chargeable lithium cell.
Background technology
Since the reducing of size and alleviating of weight of portable electric appts, thus need recently to develop the battery that is used in the portable electric appts, and require such battery not only to have high-performance but also have big capacity.
Battery produces electric power by the electrochemical reaction material (abbreviating " active material " hereinafter as) that use is used to form anodal and negative pole.Embed/take off in the embedding process at anodal and negative pole at lithium ion, chargeable lithium cell is because the variation of chemical potential produces electric energy.
In the disclosed above-mentioned information of this background technology part only is in order to strengthen the understanding to technical background of the present invention, so it may comprise this country information of known systems for those of ordinary skills that is not formed in.
Summary of the invention
One embodiment of the present of invention provide a kind of method for preparing positive electrode active materials, and described positive electrode active materials is cost-effective, and have good stable, higher capacity, the conductance of raising and the multiplying power property of Geng Gao.
According to an aspect of the present invention, a kind of preparation method that is used for the positive electrode active materials of chargeable lithium cell may further comprise the steps: stove a) is provided and is contained in the crucible of described stove; B) mixture with composition metal predecessor and lithium compound is put in the described crucible; And c) prepares the positive electrode active materials that is used for chargeable lithium cell by the described mixture in the described crucible of roasting.At technology b) in the process, the minimum range that the described mixture in the described crucible is placed as the outside of the described mixture making from the optional position of the inside of described mixture to described crucible is about 5cm or littler.
At technology b) in the process, the described mixture in the described crucible can have the about 5cm that measures from the bottom of described crucible or littler height.
At technology b) in the process, the described mixture in the described crucible can have the about 3cm that measures from the bottom of described crucible or littler height.
At technology b) afterwards and at technology c) before, also form in the described mixture in described crucible and have the predetermined gap or the groove of the degree of depth.
Form the predetermined gap or the degree of depth in the described mixture in described crucible, make from the optional position of the inside of described mixture the minimum range of the outside of described mixture or can be about 5cm or littler to the minimum range of described groove from the optional position of the inside of described mixture.
The positive electrode active materials that is used for chargeable lithium cell can comprise the lithium metal oxide of being represented by following Chemical formula 1.
[Chemical formula 1]
Li aMeO 2
In Chemical formula 1, Me is Ni xCo yMn zM ' k, 0.45≤x≤0.65,0.15≤y≤0.25,0.15≤z≤0.35,0.9≤a≤1.2,0≤k≤0.1, x+y+z+k=1, and M ' is Al, Mg, Ti, Zr or their combination.
In Chemical formula 1,0.55≤x≤0.65,0.15≤y≤0.25,0.15≤z≤0.25,0≤k≤0.1, and x+y+z+k=1.
In Chemical formula 1, y and z can be identical.
Can be with technology b) described composition metal predecessor and described lithium compound mix, make the metal of described composition metal predecessor and the lithium of described lithium compound to exist with about 0.9 to about 1.2 mol ratio.
In one embodiment, the mol ratio of the lithium of the metal of described composition metal predecessor and described lithium compound can be about 0.97 to about 1.05.
The scope of sintering temperature technology c) can be for more than or equal to about 800 ℃ and smaller or equal to about 900 ℃.
The scope of sintering temperature technology c in one embodiment) can be about 850 ℃ to about 890 ℃.
Lithium compound can comprise lithium carbonate, lithium nitrate, lithium acetate, lithium hydroxide, hydronium(ion) oxidation lithium, lithia or their combination.
At technology c) in, the air that is positioned at the upside of described stove can satisfy following equation 1:
[equation 1]
Air influx (the m of x={ per unit hour 3/ h) }/{ internal capacity (m of stove 3)
In equation 1,1.0≤x≤100.0.
In another aspect of the present disclosure, a kind of chargeable lithium cell is provided, described chargeable lithium cell comprises positive pole, negative pole and electrolyte, wherein, described positive pole comprises collector and the anode active material layer that is arranged on the described collector, and described anode active material layer comprises the positive electrode active materials of making by above method.
Of the present disclosure another aspect in, a kind of chargeable lithium cell is provided, described chargeable lithium cell comprises positive pole, negative pole and electrolyte, described positive pole comprise raman spectrum strength than I (587)/I (567) greater than about 1.02 positive electrode active materials.
The raman spectrum strength of described positive electrode active materials can be greater than about 1.02 and smaller or equal to about 1.08 than I (587)/I (567).
Described electrolyte can comprise non-aqueous organic solvent and lithium salts.
Described chargeable lithium cell can also comprise separator.
Described separator can be for being selected from the single or multiple lift separator of polyethylene, polypropylene or poly-inclined to one side vinylidene fluoride.
Described positive electrode active materials is cost-effective, has good stable, higher capacity, the conductance of raising and the multiplying power property of Geng Gao.
Description of drawings
Detailed description when considering below in conjunction with accompanying drawing by reference, the present invention becomes and is easier to understand, simultaneously to more complete understanding of the present invention and many subsidiary advantages of the present invention will become be easy to apparent, in the accompanying drawings, the identical identical or similar assembly of label indication, wherein:
Fig. 1 is the schematic diagram that the mixture 102 that is arranged in the crucible 101 is shown;
Fig. 2 is the SEM photo that illustrates according to the positive electrode active materials of example 1 preparation;
Fig. 3 is the SEM photo according to the positive electrode active materials of comparative examples 1 preparation;
Fig. 4 is the Raman analysis data of example 1 and comparative examples 1;
Fig. 5 is the schematic diagram according to the chargeable lithium cell of an embodiment; And
Fig. 6 is the flow chart that the manufacturing process of the positive electrode active materials that is used for chargeable lithium cell is shown.
Embodiment
The chargeable lithium cell use reversibly embeds in charging and exoelectrical reaction process or the material of removal lithium embedded ion is used for positive electrode active materials and negative active core-shell material, and chargeable lithium cell comprises organic electrolyte solution or polymer dielectric between positive pole and negative pole.
For the positive electrode active materials of chargeable lithium cell, used the lithium complex metal compound, and after deliberation such as LiCoO 2, LiMn 2O 4, LiNiO 2, LiNi 1-xCo xO 2(0≤x≤1), LiMnO 2Deng lithium complex metal oxide.
In positive electrode active materials, based on the positive electrode active materials of manganese LiMn for example 2O 4Or LiMnO 2The easiest to be synthetic, cost is lower than other material, compare with other active material during overcharging, to have excellent thermal stability, and environmentally friendly.
Yet these capacity based on the material of manganese are relatively low.
In business-like positive electrode active materials, because LiCoO 2Have conductance preferably, the approximately higher cell voltage, excellent cycle life characteristics, advantages of higher stability and excellent discharge capacity of 3.7V, so LiCoO 2Give prominence to.Yet, because LiCoO 2Be expensive, and shared cost be the battery total cost 30% or more, so LiCoO 2Aspect cost, has inferior position.
In addition, in the positive electrode active materials of mentioning, LiNiO 2Have the highest discharge capacity battery behavior, but LiNiO 2Be difficult to synthesize.In addition, the high oxidation state of nickel can cause the cycle life deterioration of battery and electrode, and can cause the low invertibity of easy self discharge of battery and battery.In addition, because be difficult to guarantee the stability of battery, so be difficult to make commercially available battery.
To describe embodiments of the invention in detail hereinafter.Yet these embodiment only are exemplary, the invention is not restricted to this.
In one embodiment, as shown in Figure 6, provide preparation to be used for the method for the positive electrode active materials of chargeable lithium cell.This method may further comprise the steps: stove and the crucible (S1) that is contained in the stove a) are provided; B) mixture with composition metal predecessor and lithium compound is put into (S2) in the crucible; And c) prepares the positive electrode active materials (S3) that is used for chargeable lithium cell by the mixture in the roasting crucible.At technology b) in, to be placed as the minimum range that makes from the optional position of the inside of mixture to the outside that is arranged on the mixture the crucible be about 5cm or littler with being arranged on mixture in the crucible.
When being about 5cm or more hour to the minimum range of the outside of mixture, can reduce the carbon dioxide that during roasting technique, produces effectively from the optional position of the inside of mixture.When carbon dioxide is retained in this mixture, can produce Li by being included in the lithium compound in this mixture and the reaction of carbon dioxide 2CO 3The accessory substance of type.The Ni that concentrates in the composition metal predecessor is many more, and the problem that produces accessory substance is just serious more.
This preparation method can also be included in the technology that forms groove in the mixture in the crucible with the predetermined gap or the predetermined degree of depth.By the groove that forms, can remove the carbon dioxide that during roasting, produces effectively.
Fig. 1 shows the mixture 102 in the crucible 101.Crucible 101 is arranged in the stove 100.In one embodiment, mixture 102 can directly contact with the bottom B of crucible 101.The height of mixture 102 is represented by h.In one embodiment, can measure the height of mixture 102 from the bottom B of crucible 101.Mixture 102 can comprise predetermined groove 103, and groove can exist a plurality of.In one embodiment, the height of groove 103 can be identical with the height of mixture 102.In addition, can control the height h ' and the width w of groove 103 as required.
Groove 103 can have about 1cm extremely approximately height and the width of about 0.1cm to about 1cm of 10cm.In addition, between adjacent groove 103, can have the gap g of about 1cm, and the repetition period of gap g can be about 1 to about 50 to about 10cm.
As mentioned above, when being about 5cm or more hour to the minimum range of the outside of mixture 102, can remove produced simultaneously carbon dioxide effectively at roasting mixture 102 from the optional position of the inside of mixture.If do not remove carbon dioxide effectively from the inside of mixture 102, lithium compound (for example, Li then 2CO 3) can not decompose fully, therefore, can produce Li by the reaction that is included in lithium compound in the mixture and carbon dioxide 2CO 3The accessory substance of type.The Ni that concentrates in the composition metal predecessor is many more, and the problem that produces accessory substance is just serious more.
Groove 103 can be formed and make from the optional position of the inside of mixture 102 minimum range of the outside of mixture 102 or can be about 5cm or littler to the minimum range of groove 103 from the optional position of the inside of mixture 102.In one embodiment, minimum range can be about 3cm or littler.
With reference to Fig. 1, a and a ' are meant two optional positions of the inside of mixture 102.When an optional position is a, figure 1 illustrates the minimum range of the outside of mixture 102.In other words, minimum range da can be the distance of 103 the side from position a to groove.When another optional position is a ' time, be that position a ' is to the distance between the top surface TS of mixture 102 to the minimum range da ' of the outside of mixture 102.
When the minimum range from an optional position to the outside of mixture is about 5cm or more hour, discharge carbon dioxide above-mentioned easily.In one embodiment, minimum range can be in about 3cm.
In one embodiment, at least one position that is arranged in the mixture 102 has to the minimum range on the surface of mixture 102, and such minimum range can be about 5cm or littler.In another embodiment, such minimum range can be in about 3cm.
At technology b) in, the height (h) of the mixture 102 in the crucible 101 can be about 5cm or littler.In one embodiment, highly (h) can be about 3cm or littler.When the minimum range from an optional position to the outside of mixture 102 is in about 5cm or littler scope, can remove the carbon dioxide that during roasting technique, produces effectively.When height h was about 5cm, the minimum range from an optional position to the outside of mixture 102 can be about 5cm or littler.
The positive electrode active materials that is used for chargeable lithium cell can comprise the lithium metal oxide of being represented by following Chemical formula 1.
[Chemical formula 1]
Li aMeO 2
In Chemical formula 1, Me is Ni xCo yMn zM ' k, 0.45≤x≤0.65,0.15≤y≤0.25,0.15≤z≤0.35,0.9≤a≤1.2,0≤k≤0.1, x+y+z+k=1, and M ' can be Al, Mg, Ti, Zr or their combination.
In Chemical formula 1,0.55≤x≤0.65,0.15≤y≤0.25,0.15≤z≤0.25,0≤k≤0.1, and x+y+z+k=1.Ni, Co and Mn can be at about Ni: Co: Mn=6: in 2: 2 the mol ratio.This mol ratio exceeds the mol ratio of general ternary system positive electrode active materials, and such mol ratio can be improved battery behavior, for example battery capacity, voltage confining force, cycle characteristics etc.
More particularly, in Chemical formula 1, y and z can be identical.In other words, Co can have identical mol ratio with Mn.In the time of in positive electrode active materials is included in above-mentioned scope, can improve battery capacity, cycle life, stability etc.
Can make positive electrode active materials be doped with Al, Mg, Ti, Zr or their combination by control k value.By mixing in suitable scope inner control, chargeable lithium cell can have good high magnification characteristic and initial capacity.
When the positive electrode active materials of the composition with Chemical formula 1 less is exposed to air (oxygen), can produce the phase of not expecting, and then aspect battery capacity, cause harmful effect, and the general positive electrode active materials based on Co does not have this phase of not expecting.
Can hybrid technique b) composition metal predecessor and lithium compound, make the mol ratio of lithium of the metal of composition metal predecessor and lithium compound to be about 0.9 to about 1.2.In one embodiment, mol ratio can be from about 0.97 to about 1.05 scope.When the mol ratio of lithium and transition elements is in this scope, can improve battery capacity.
Technology c) sintering temperature can about 800 ℃ or higher and less than about 900 ℃ between.In one embodiment, sintering temperature can be about 850 ℃ to about 890 ℃.Can carry out roasting technique by to about 20 ℃/minute heating rate temperature being increased to top sintering temperature with about 0.5 ℃/minute.This temperature range can be lower than general sintering temperature scope.When in this scope, carrying out roasting, can control grain shape as well as possiblely, and can make maximum capacity.
For example, in order to improve the battery capacity characteristic, the predecessor based on the positive electrode active materials of Ni that contains 60mol% or more Ni based on the total metal that is included in the 100mol% in the predecessor need carry out roasting less than about 900 ℃ temperature.
Lithium compound can comprise lithium carbonate, lithium nitrate, lithium acetate, lithium hydroxide, hydronium(ion) oxidation lithium, lithia or their combination, but is not limited thereto.
At technology c) in, the air that is positioned at the upside of stove can satisfy following equation 1.
[equation 1]
Air influx (the m of x={ per unit hour 3/ h) }/{ internal capacity (m of stove 3)
In equation 1,1.0≤x≤100.0.
Here, the air that is positioned at the top of stove can have the momentum that satisfies equation 1.Therefore, can easily remove carbon dioxide above-mentioned.
In another embodiment, chargeable lithium cell can comprise positive pole, negative pole and electrolyte, and wherein, positive pole comprises collector and the anode active material layer that is arranged on the collector, and anode active material layer comprises positive electrode active materials.
Because positive electrode active materials is identical with above-described embodiment, so will no longer describe positive electrode active materials hereinafter.
In another embodiment, the raman spectrum strength of positive electrode active materials than I (587)/I (567) greater than about 1.02.In another embodiment, raman spectrum strength can be greater than about 1.02 and smaller or equal to about 1.08 (that is, 1.02＜raman spectrum strength is than I (587)/I (567)≤1.08) than I (587)/I (567).The raman spectrum strength ratio is that I (587) is (at about 587cm -1The height at peak at place) with I (567) (at about 567cm -1The height at the peak at place) strength ratio.
Anode active material layer can comprise binding agent and electric conducting material.
Binding agent improves the positive electrode active materials particle binding ability to each other and the binding ability of positive electrode active materials particle and collector.The example of binding agent comprises from by polyvinyl chloride, the polyvinyl fluoride of polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinyl chloride, carboxylation, the polymer that contains ethylidene oxygen, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, poly-inclined to one side 1, that selects in the group of compositions such as the butadiene-styrene rubber that 1-difluoroethylene, polyethylene, polypropylene, butadiene-styrene rubber, acrylic acid (ester) are changed, epoxy resin, nylon is at least a, but is not limited thereto.
Comprise that electric conducting material improves electrode conductivity.Can use any electric conducting material as this electric conducting material, unless it causes chemical change.The example of electric conducting material comprises: based on the material of carbon, and for example native graphite, Delanium, carbon black, acetylene black, Ketjen black, carbon fiber etc.; Based on the material of metal, for example comprise the metal powder or the metallic fiber of copper, nickel, aluminium, silver etc.; Conducting polymer, for example polyphenylene derivative; Perhaps their mixture.
Negative pole comprises collector and the anode active material layer that is arranged on the collector, and anode active material layer comprises negative active core-shell material.
Negative active core-shell material can comprise embedding/removal lithium embedded ion reversibly material, lithium metal, lithium metal alloy, can mix and the material or the transition metal oxide of dedoping lithium.
Reversibly the material of embedding/removal lithium embedded ion comprises material with carbon element.Material with carbon element can be any normally used negative active core-shell material based on carbon that is used for lithium ion chargeable battery.The example of material with carbon element comprises crystalline carbon, amorphous carbon or their mixture.Crystalline carbon can be unbodied or sheet shape, lamelliform, spherical or fibrous native graphite or Delanium.Amorphous carbon can be soft carbon, hard carbon, mesophase pitch carbide, calcined coke (fired coke) etc.
The metal that the example of lithium metal alloy comprises lithium and is selected from Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al or Sn.
Can mix and the example of the material of dedoping lithium comprises Si, SiO x(0＜x＜2), Si-Q alloy (wherein, Q is the element that is selected from the group of being made up of alkali metal, alkaline-earth metal, 13 family's elements, 14 family's elements, transition elements, rare earth element and their combination, and is not Si), Sn, SnO 2, Sn-Q alloy (wherein, Q is the element that is selected from the group of being made up of alkali metal, alkaline-earth metal, 13 family's elements, 14 family's elements, transition elements, rare earth element and their combination, and is not Sn) and their mixture.Can be with at least a and SiO in these materials 2Mix.Element Q is selected from Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, Se, Te, Po or their combination.
The example of transition metal oxide comprises barium oxide, lithium-barium oxide etc.
Anode active material layer comprises binding agent, and comprises electric conducting material alternatively.
Binding agent improves the negative active core-shell material particle binding ability to each other and the binding ability of negative active core-shell material particle and collector, and binding agent comprises polyvinyl chloride, polyvinyl fluoride, poly(ethylene oxide), polyvinylpyrrolidone, polyurethane, the polytetrafluoroethylene, poly-inclined to one side 1 of polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinyl chloride, carboxylation, butadiene-styrene rubber, epoxy resin or nylon that 1-difluoroethylene, polyethylene, polypropylene, butadiene-styrene rubber, acrylic acid (ester) are changed, but be not limited thereto.
Comprise that electric conducting material improves electrode conductivity.Can use any electric conducting material as this electric conducting material, unless it causes chemical change.The example of electric conducting material comprises: based on the material of carbon, and for example native graphite, Delanium, carbon black, acetylene black, Ketjen black, carbon fiber etc.; Based on the material of metal, comprise the metal powder or the metallic fiber of copper, nickel, aluminium, silver etc.; The conducting polymer of polyphenylene derivative; Perhaps their mixture.
Collector can be selected from Copper Foil, nickel foil, stainless steel foil, titanium foil, nickel foam, foam copper, the polymeric substrates that is covered with conducting metal or their combination.
Collector can comprise Al, but is not limited thereto.
Negative pole and positive pole can followingly be made: negative active core-shell material, electric conducting material and binding agent are blended in the solvent, with the preparation active material composite; And active material composite is coated on the collector.Electrode manufacturing method is known, therefore is not described in detail in this manual.Solvent can comprise N-methyl pyrrolidone etc., but is not limited thereto.
Electrolyte can comprise non-aqueous organic solvent and lithium salts.
Non-aqueous organic solvent plays the effect of transmitting the ion relevant with the electrochemical reaction of battery.
Non-aqueous organic solvent can comprise carbonates solvent, esters solvent, ether solvent, ketones solvent, alcohols solvent or aprotic solvent.The example of carbonates solvent comprises dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), carbonic acid first propyl ester (MPC), ethyl propyl carbonic acid ester (EPC), methyl ethyl carbonate (MEC), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and the example of esters solvent comprises methyl acetate, ethyl acetate, n-propyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, gamma-butyrolacton, decalactone, valerolactone, mevalonolactone, caprolactone etc.The example of ether solvent can comprise butyl oxide, tetraethylene glycol dimethyl ether, diethylene glycol dimethyl ether, glycol dimethyl ether, 2-methyltetrahydrofuran, oxolane etc., and the example of ketones solvent can comprise cyclohexanone etc.The example of alcohols solvent can comprise ethanol, isopropyl alcohol etc., and the example of aprotic solvent can comprise that (wherein, R is C to R-CN 2To C 20Straight-chain alkyl, branched hydrocarbyl or cyclic hydrocarbon radical, two key, aromatic rings or ehter bond), acid amides (for example, dimethyl formamide), dioxolanes (for example, 1,3-dioxolanes), sulfolane etc.
Non-aqueous organic solvent can use individually or use with the form of mixture.When with an organic solvent the time, controlling mixing ratio according to the battery performance of expectation with the form of mixture.
The carbonates solvent can comprise the mixture of cyclic carbonate and linear carbonate.Cyclic carbonate and linear carbonate mixed to about 1: 9 volume ratio with about 1: 1, when using this mixture as non-aqueous organic solvent, can strengthen the electrolyte performance.
In addition, the electrolyte of an embodiment can also comprise the mixture of carbonates solvent and aromatic hydrocarbon solvent.Carbonates solvent and aromatic hydrocarbon solvent mixed to about 30: 1 volume ratio with about 1: 1.
The arene organic solvent can be represented by following Chemical formula 2.
[Chemical formula 2]
In Chemical formula 2, R 1To R 6Can be identical or different, and can be independently selected from hydrogen, halogen, C 1To C 10Alkyl, C 1To C 10Haloalkyl or their combination.
The example of arene organic solvent comprises benzene, fluorobenzene, 1, the 2-difluoro-benzene, 1, the 3-difluoro-benzene, 1, the 4-difluoro-benzene, 1,2, the 3-trifluoro-benzene, 1,2, the 4-trifluoro-benzene, chlorobenzene, 1, the 2-dichlorobenzene, 1, the 3-dichlorobenzene, 1, the 4-dichlorobenzene, 1,2, the 3-trichloro-benzene, 1,2, the 4-trichloro-benzene, iodobenzene, 1, the 2-diiodo-benzene, 1, the 3-diiodo-benzene, 1, the 4-diiodo-benzene, 1,2, the 3-phenyl triiodide, 1,2, the 4-phenyl triiodide, toluene, fluorotoluene, 2,3-two fluoro toluene, 2,4-two fluoro toluene, 2,5-two fluoro toluene, 2,3,4-three fluoro toluene, 2,3,5-three fluoro toluene, chlorotoluene, 2,3-dichloro-toluene, 2,4-dichloro-toluene, 2,5-dichloro-toluene, 2,3,4-three chloro toluene, 2,3,5-three chloro toluene, iodo toluene, 2,3-two iodo toluene, 2,4-two iodo toluene, 2,5-two iodo toluene, 2,3,4-three iodo toluene, 2,3,5-three iodo toluene, dimethylbenzene or their combination.
In order to improve the cycle life of battery, nonaqueous electrolyte can also comprise the ethylene carbonate compounds of vinylene carbonate or following chemical formula 3.
[chemical formula 3]
In chemical formula 3, R 7And R 8Identical or different, and can be independently selected from hydrogen, halogen, cyano group (CN), nitro (NO 2) or C 1To C 5As long as fluoro-alkyl is R 7And R 8In at least one be halogen, cyano group (CN), nitro (NO 2) or C 1To C 5Fluoro-alkyl.
The ethylene carbonate compounds comprises carbonic acid two fluoro ethyls, carbonic acid chloro ethyl, carbonic acid dichloro-ethyl, carbonic acid bromo ethyl, carbonic acid two bromo ethyls, carbonic acid nitro ethyl, carbonic acid cyano group ethyl or carbonic acid fluoro ethyl.Can in suitable scope, regulate the consumption of this additive that is used to improve cycle life.
Lithium salts provides lithium ion in battery, and makes the basic operation operation of chargeable lithium cell, and improves the transmission of lithium ion between positive pole and negative pole.The non-limiting example of lithium salts comprises from LiPF 6, LiBF 4, LiSbF 6, LiAsF 6, LiN (SO 2C 2F 5) 2, Li (CF 3SO 2) 2N, LiN (SO 3C 2F 5) 2, LiC 4F 9SO 3, LiClO 4, LiAlO 2, LiAlCl 4, LiN (C xF 2x+1SO 2) (C yF 2y+1SO 2) (wherein x and y are natural numbers), LiCl, LiI and LiB (C 2O 4) 2(dioxalic acid lithium borate, LiBOB) the middle at least a support salt of selecting.Can be with the concentration use lithium salts of about 0.1M (mol/L) to about 2.0M.When comprising lithium salts, can improve electrolyte performance and lithium ion mobility owing to the electrolyte conductivity and the viscosity of the best with above-mentioned concentration range.
As required, chargeable lithium cell can also comprise the separator that is arranged between negative pole and the positive pole.The non-limiting example of suitable separator material comprises polyethylene, polypropylene, poly-inclined to one side 1,1-difluoroethylene and their multilayer, for example, the double-deck separator of polyethylene/polypropylene, three layers of separator of polyethylene/polypropylene/polyethylene and three layers of separator of polypropylene, polyethylene/polypropylene.
According to the existence of separator and the electrolytical kind of in battery, using, chargeable lithium cell can be divided into lithium ion battery, lithium ion polymer battery and lithium polymer battery.Chargeable lithium cell can have different shape and size, and comprises column type, prismatic or coin type battery, and can be hull cell or can be quite big dimensionally.The structure and the manufacture method that belong to lithium ion battery of the present disclosure are known in the art.
Fig. 5 is the schematic diagram of the exemplary configuration of chargeable lithium cell.Fig. 5 shows chargeable lithium cell 1, and chargeable lithium cell 1 comprises the containment member 6 of positive pole 4, negative pole 2, battery container 5 and sealed cell housing 5, and battery container 5 comprises the electrolyte solution that floods separator 3, and separator 3 is arranged between positive pole 4 and the negative pole 2.
The present invention will be described in more detail for following example.Yet these examples should not be interpreted as limiting the scope of the invention in all senses.
Example
Example 1: the preparation of positive electrode active materials
Mix about 25.1g NiSO quantitatively 4, about 8.7g CoSO 4With about 5.2g MnSO 4, and make their reactions continuously in coprecipitater.
In reaction temperature is when about 40 ℃ and mixing speed are about 600rpm, to make coprecipitation reaction 8 hours.
Collect the transition elements predecessor hydroxide that generates by reaction, and the washing several times, and in baking oven, carry out drying with about 120 ℃.With Li 2CO 3Join in the dry transition elements predecessor hydroxide of crossing, reach till about 1.03, and use blender that mixture is mixed up to Li/ transition elements ratio.
The mixture of preparation is put in the crucible in the stove with the height of about 6cm, and forms groove, the width of described groove is about 0.5cm, is about 3cm highly, and the gap between groove is about 3cm.With about 2 ℃/minute heating rate mixture is heat-treated to about 850 ℃ temperature, at about 850 ℃ roasting temperature about 10 hours, and cool off with about 2 ℃/minute rate of temperature fall, thereby prepare positive electrode active materials.
Comparative examples 1: the preparation of positive electrode active materials
Except being placed in crucible with the height of about 6cm mixture and not having the groove, use the method identical to prepare positive electrode active materials with the method for example 1.
Example 2: the preparation of semi-simple body battery (Half-Cell)
By with the positive electrode active materials of example 1, poly-inclined to one side vinylidene fluoride binding agent and carbonaceous conductive agent with about 96: about 2: about 2 weight ratio is dispersed in the N-crassitude ketone solvent and prepares anode sizing agent.Be prepared as follows positive pole: anode sizing agent is coated on the aluminium foil that thickness is about 60 μ m to form the thin electrodes plate, in about 3 hours of about 135 ℃ of dryings or longer time, and compacting thin electrodes plate.
Be prepared as follows semi-simple body battery: use this positive pole and as to the lithium metal of electrode, the sub polyethylene spacing body is arranged on positive pole and, and inject electrolyte between the electrode.For electrolyte, using and being dissolved in volume ratio is 1.3M LiPF in 2: 2: 6 the mixed solvent of ethylene carbonate (EC), ethylene methyl esters (EMC) and dimethyl carbonate (DMC) 6
Comparative examples 2: the preparation of semi-simple body battery
Except the positive electrode active materials that uses comparative examples 1 replaces the positive electrode active materials of example 1, use the method identical to make semi-simple body battery with the method for example 2.
Experimental example
Scanning electron microscopy (SEM)
Fig. 2 is scanning electron microscopy (SEM) photo according to the positive electrode active materials of example 1 preparation, and Fig. 3 is the SEM photo according to the positive electrode active materials of comparative examples 1 preparation.Fig. 2 and Fig. 3 have amplified about 20,000 times.
As shown in Fig. 2 and Fig. 3, in positive electrode active materials, because Li according to the comparative examples 1 that does not form groove 2CO 3Carbon dioxide be difficult to successfully remove, so Li 2CO 3Stay on the surface of particle with other compound based on Li.On the contrary, compare with comparative examples 1, the positive electrode active materials of example 1 has the more surface of homogeneous.
Therefore, the positive electrode active materials of example 1 can form the LiNi of homogeneous xCo yMn zO 2Phase can provide excellent battery behavior thus.
Raman analysis
Carry out Raman analysis under the following conditions.
Analysis condition: Ar +Laser (514.5nm), power=1mW, time=300s, multiplication factor=50X.
Fig. 4 shows the result of the Raman analysis of example 1 and comparative examples 1.
Compare with example 1, comparative examples 1 shows at about 567cm -1The peak intensity increase tendency at place.In addition, the raman spectrum strength of the positive electrode active materials of example 1 is about 1.066 than I (587)/I (567), and the raman spectrum strength of the positive electrode active materials of comparative examples 1 is about 1.02 than I (587)/I (567), as shown in Figure 4.These the possibility of result are by Li 2CO 3Carbon dioxide do not remove fully and by being included in the reaction generation Li of lithium compound and carbon dioxide in the mixture 2CO 3The fact of the accessory substance of type causes.
The battery cell characteristic
Battery cell characteristic according to the semi-simple body battery of example 2 and comparative examples 2 preparations has been shown in the table 1 below.
Table 1
Figure BSA00000503751900131
As shown in table 1, what know is, compares with comparative examples 2, and the efficiency for charge-discharge of example 2 and multiplying power-performance are excellent more.
Though in conjunction with the current content description that is regarded as actual exemplary embodiment the disclosure, but be to be understood that, the disclosure is not limited to the disclosed embodiments, but opposite, and disclosure intention covers various modifications and the equivalent arrangements in the spirit and scope that are included in claim.Therefore, embodiment above-mentioned is exemplary, and is not construed as limiting in all senses.

Claims (20)

1. method for preparing the positive electrode active materials that is used for chargeable lithium cell, described method comprises:
A) provide stove and the crucible that is arranged in the described stove;
B) mixture with composition metal predecessor and lithium compound is put in the described crucible; And
C) prepare the positive electrode active materials that is used for chargeable lithium cell by the described mixture in the described crucible of roasting,
Wherein, at technology b) in, be 5cm or with being arranged on minimum range that described mixture in the described crucible is placed as the outside of the described mixture making from the optional position of the inside of described mixture to described crucible less than 5cm.
2. method according to claim 1, wherein, described mixture has the 5cm that measures from the bottom of described crucible or less than the height of 5cm.
3. method according to claim 1, wherein, described mixture has the 3cm that measures from the bottom of described crucible or less than the height of 3cm.
4. method according to claim 1, described method also comprises following technology: after described mixture being put in the described crucible and before the described mixture of roasting, formation has the predetermined gap and the groove of the degree of depth in the described mixture in being arranged on described crucible.
5. method according to claim 4, wherein, form in the described mixture in being arranged on described crucible and have the described predetermined gap and the described groove of the degree of depth, make from the described optional position of the inside of described mixture that the described minimum range of the outside of described mixture is 5cm or less than 5cm, perhaps
Is 5cm or less than 5cm from the described optional position of the inside of described mixture to the minimum range of described groove.
6. method according to claim 1, wherein, described positive electrode active materials comprises the lithium metal oxide of being represented by following Chemical formula 1:
Li aMeO 2，
Wherein, Me is Ni xCo yMn zM ' k, 0.45≤x≤0.65,0.15≤y≤0.25,0.15≤z≤0.35,0.9≤a≤1.2,0≤k≤0.1, x+y+z+k=1, and M ' is Al, Mg, Ti, Zr or their combination.
7. method according to claim 6, wherein, in Chemical formula 1,0.55≤x≤0.65,0.15≤z≤0.25.
8. method according to claim 7, wherein, y is identical with z.
9. method according to claim 1 is wherein, with described technology b) described composition metal predecessor and described lithium compound mix, make that the mol ratio of lithium of the metal of described composition metal predecessor and described lithium compound is 0.9 to 1.2.
10. method according to claim 9, wherein, the mol ratio of the described metal of described composition metal predecessor and the lithium of described lithium compound is 0.97 to 1.05.
11. the scope of sintering temperature method according to claim 1, wherein, technology c) is 800 ℃ or higher and less than 900 ℃.
12. the scope of sintering temperature method according to claim 11, wherein, technology c) is 850 ℃ to 890 ℃.
13. method according to claim 1, wherein, described lithium compound comprises lithium carbonate, lithium nitrate, lithium acetate, lithium hydroxide, hydronium(ion) oxidation lithium, lithia or their combination.
14. method according to claim 1, wherein, at technology c) in, the air that is positioned at the upside of described stove satisfies following equation:
The air influx of x={ per unit hour }/{ internal capacity of stove }
Wherein, 1.0≤x≤100.0, the unit of the air influx of described per unit hour is m 3/ h, the unit of the internal capacity of described stove are m 3
15. a chargeable lithium cell, described chargeable lithium cell comprises positive pole, negative pole and electrolyte,
Wherein, described positive pole comprises collector and the anode active material layer that is arranged on the described collector, and described anode active material layer comprises the positive electrode active materials of making by method according to claim 1.
16. chargeable lithium cell according to claim 15, wherein, described electrolyte comprises non-aqueous organic solvent and lithium salts.
17. chargeable lithium cell according to claim 15, wherein, described chargeable lithium cell also comprises the separator that is arranged between described negative pole and the described positive pole.
18. chargeable lithium cell according to claim 17, wherein, described separator is the single or multiple lift separator that is selected from polyethylene, polypropylene or poly-inclined to one side vinylidene fluoride.
19. a chargeable lithium cell, described chargeable lithium cell comprises:
Positive pole, comprise raman spectrum strength than I (587)/I (567) greater than 1.02 positive electrode active materials;
Negative pole; And
Electrolyte.
20. chargeable lithium cell according to claim 19, described raman spectrum strength is than I (587))/I (567) is greater than 1.02 and smaller or equal to 1.08.
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